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I understand that combinations like Skarmory+Blissey are powerful in singles, but why do people use them in doubles, where the physical sweepers can attack the special walls, and vice versa?

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Um... they don't? I'll be honest, I've been into doubles for a couple of months now and can safely say that I've never seen a SkarmBliss combo against a serious player.
Doubles is waaaaaayyy more Hyper Offense than Singles, seeing as battles take 8-11 turns on average. Are you asking this question for VGC or Smogon Doubles, or just double battling in general?
any competitive doubles battle

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Defense synergy doesn't exist in doubles, I don't know what you're talking about :x

And no, I don't recall having heard of people running SkarmBliss in doubles. I am sure it's obvious, but here's everything wrong with defensive synergy in doubles. I know every last one of these points is ridiculously long, so there's a TL;DR at the end of each one :P

  • Team play in singles favors switching to gain momentum, and hence mono-defensive Pokemon (specializing in one defense and sucking at the other) tend to co-ordinate well by cycling around. In doubles though, switching too much means that your Pokemon loses a turn, and both the opponent's Pokemon get the opportunity to hammer into one target (maybe even knocking out one of your Pokemon). Granted this can be remedied by prediction (and certain scenarios make ideal switch situations), but seeing the better options all around, I don't see why someone would adopt this.
    TL;DR: Limited switching means limited effectiveness of defensive synergy.

  • Defensive synergy more than often involves external means of damage (Toxic, Leech Seed, weather, etc). One thing: the value of one turn in doubles is much more than that in singles. Four Pokemon move simultaneously on that one turn, meaning that the offense is obviously increased (two attackers). Question - why would someone want to whittle down the opponent's HP when flat out attacking does the job much faster? You take out a measly 1/8th of your opponent's health, while the opponent is out on a killing spree, poking gaping holes across your health; all in that one turn. It's you who is at the losing end of this.
    Exception being Leech Seed because you gain health and damage at the same time. Pokemon that adhere to Leech Seed stalling - Ferrothorn and M-Venusaur.
    TL;DR: They are too static to work in a doubles environment.

  • As a continuation to my previous point. Offense obviously increases with two attackers on the field, but make no mistake: the individual defense of each Pokemon remains the same. Defensive or not, nothing will last on it's own on the field, especially if both opposing Pokemon are attackers. And with their lol-worthy offenses, most defense-cores can get hammered while being unable to retaliate well enough.
    TL;DR: Due to offense being greater than defense at all times, defensive cores can't do the one thing they were built for: take hits.

  • ★Like I mentioned earlier, defensive cores usually involve two Pokemon that specialize in defense and special defense to cover up for each other's faulty defense stat. Like you said in the question, two Pokemon means more modes of attack for your opponent. Hence self-sufficient Pokemon like Gyarados and Cresselia (with well-rounded stats) are preferred. This is also the reason why so many complex spreads exist in VGC; they primarily increase a Pokemon's self sufficiency so that when all individual Pokemon come together, they can function at their highest.
    TL;DR: The monochromatic pattern of Pokemon forming a defensive core is frowned upon in doubles.

PS: Defensive Pokemon are often reserved as utility Pokemon, like setting Trick Room, Tailwind, Perish-Trap, speed control etc. There are exceptions however, like Mega Venusaur (but they only exist because their offensive potential is usable).

Defensive cores do exist, but their purpose is not just to take hits, but also dish them out on the opponent (courtesy of Astro for reminding me). This could be translated as bulky offense at the end of the day, but that's how defensive synergy is like in doubles. Nowhere near the singles defense cores like SkarmBliss, which is what you meant in question.

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Oh, thank you for answering this. I was racking my brain trying to figure out a way to explain why defensive cores aren't good in Doubles. Sometimes it's hard for me to transition my thoughts into words :P

I just want to make one connection with Point #2 and the italicized P.S.: Leech Seed stalling can actually work in Doubles/VGC, although pretty much exclusive to Ferrothorn and Mega Venusaur. This is because they are both bulky as heck and can dish out damage as well, meaning that they can afford to run pseudo-Stall. A Venusaur or Ferrothorn on the field, even alone, with double Leech Seed and no checks left on your side can be a real bulldozer.

Here's my two bits about the whole thing, which I'm not gonna write as an answer.

In Doubles/VGC, there is such a thing as a defensive switch-in. But it's different than Singles. I'll use the example of an Escavalier / Heatran / Jellicent Trick Room core. In Doubles, you want to have a resist to switch in to obvious SE attacks. However, you also want that switch-in to be able to BEAT the Pokémon firing off attacks.

In the core I listed above, we have Jellicent to set up Trick Room and Heatran and Escavalier to sweep. Jellicent hates being Spored by Amoonguss, and Amoonguss in general. So, switch in either Escavalier to take a Spore or Heatran to take a Giga Drain. However, the reason this type of defensive switching works is because both Esca and Heatran can BEAT Amoonguss, meaning that Jellicent won't have to deal with it later. If I switched in, say, Safety Goggles Swampert, I might be able to switch into a Spore, but all defensive value is lost to a consecutive Giga Drain because Swampert has no way to reliably check Amoonguss.

Likewise, Escavalier despise Fire attacks coming it's way. Hence why Heatran is on the team: to take Fire attacks via Flash Fire. However, it can also consistently DEFEAT most Fire-types with Earth Power, thus making it work as part of a defensive core. Jellicent can also remove Fire-types. Now lets' look at Jellicent's weaknesses. Dark-types are both resisted and hecked big-time by Megahorn. The aforementioned Grass-types are checked by both partners. Electric-types are handled by Earth Power and Drill Run.

Defensive cores aren't perfect. For example, Jellicent in immune to Heatran's Fighting weakness. However, the only Fighting Pokémon it can really check is Terrakion. For this reason, a Pokémon like Sylveon is added because it works in Trick Room and resists and checks Fighting-types. Her weaknesses are covered by Heatran's Fire STABs and Earth Power, as well as Esca's Drill Run.

This is what makes Doubles different than Singles. One Pokémon can't take on the world. Even three Pokémon can't do it perfectly. You have to have a team of 6-4 Pokémon that mesh together, cover each other, and can adapt to many environments.

TL;DR Defensive cores in VGC/Doubles have to have offensive capabilities as well. Pokémon like Escavalier are bulky, powerful, have a lot of resistances, and bring something to the team that supports it (Spore immunity with Overcoat). Pokémon like Blissey and Skarmory just… sit there and absorb a shot or two.
Yeah, I think I should've added a bit more clarity to the "exceptions" part for Leech Seed stallling. I didn't really add the core you gave though because I mostly thought of those as "bulky offensive cores". They do double as a defensive core though, so think I'll mention that in the answer c: (thanks for the mention)
Aegislash + Scrafty is pretty popular and is based on defensive synergy... Jus' sayin' :p
Aegislash's role is not as a defensive wall, but as a Wide Guard support and sometimes offense. Also, I just wanted to cite a friend's opinion in synergy for VGC (not smogon doubles because I'm a little off with it ^_^"). He says that there's no offensive or defensive synergy in doubles, it's all so mixed up that it just classifies as "synergy". Perhaps true, but I'm not sure.
Yeah, it's Bulky Offense. The purpose of one Pokémon is to take hits for another AND take out the threat. It just has more defensive synergy than an offensive core like Greninja + Talonflame + Landorus (not saying that's an actual core, but y'know.)